硫酸钛混凝去除无机砷(Ⅲ)的效能

使用硫酸钛作为混凝剂,研究了混凝去除As(Ⅲ)过程中溶液pH值、混凝剂投加量、砷的初始浓度以及阴离子对除砷效果的影响.硫酸钛的水解沉淀物颗粒等电点为pH =5;当pH =6时,水解沉淀物的粒径最大.在pH =5 ～8范围内,As(Ⅲ)的去除率高且基本稳定;而沉淀物颗粒Zeta电位降低较大.说明水解沉淀物Zeta电位对As(Ⅲ)的去除影响不大.混凝剂投加量为2.5 ～10 mg/L时,As (Ⅲ)的去除率随投加量的增加而显著增加;混凝剂投加量大于15 mg/L时,As(Ⅲ)去除率随混凝剂投加量的增加变化趋于平缓.水中阴离子(硅酸根和磷酸根离子)的存在会降低混凝对As (Ⅲ)的去除效率.     

竹炭吸附对硝基苯胺的过程与机理研究

研究了竹炭吸附对硝基苯胺的过程影响因子以及吸附过程的动力学、等温线和热力学。结果表明,粒径80~100目的竹炭即可实现对对硝基苯胺的高效吸附,吸附效率为95.65%。竹炭对硝基苯胺的吸附效率随溶液pH值的升高而逐渐下降,当溶液pH值超过7.0以后,下降趋势明显加快,实验条件下,溶液pH=2.0可以获得最佳吸附效果,吸附效率为95.85%,静电作用力和氢键作用力在不同溶液pH值下变化的联合作用是造成吸附效率变化的主要原因。吸附动力学研究结果表明:准二级吸附动力学模型可以很好的拟合3种不同温度下的吸附速率数据;吸附等温线研究结果表明,RedlichPeterson吸附等温线模型可以很好的拟合3种不同温度下的吸附等温线数据,说明吸附过程兼有单分子层吸附和吸附表面异质性的特点;吸附热力学计算结果表明,吉布斯自由能ΔG~0小于零,说明竹炭吸附对硝基苯胺的过程可以自发进行,吸附焓变ΔH~0小于零,说明吸附反应为放热过程,并且吸附焓变数值大于单纯由范德华力引起的吸附放热范围,说明吸附过程中存在多种作用力;吸附熵变ΔS~0大于零,说明吸附过程中体系的混乱度显著增大。     

复合分子筛去除水中氟化物的研究

通过使用复合分子筛对模拟含氟水进行静态吸附实验,研究了复合分子筛对水中氟化物的吸附性能,并分析了吸附过程中温度、pH值和停留时间等因素对分子筛除氟效率的影响。结果表明,用80 g粒径0.9 mm的分子筛处理150 mL浓度为5 mg/L的模拟含氟水,分子筛的除氟效率达到90%以上,而同样条件下天然沸石和改性涂铁沸石的去除率分别为23.35%和80.69%。分子筛的除氟效率随着温度呈现先上升后下降的趋势,50℃时去除效率达到最高,为92.7%;在弱酸性条件下的去除率比碱性条件要高,在pH=4时去除率最大,为91.8%;停留时间初始阶段与去除率保持正相关,在45 min后反应达到平衡。分子筛的吸附速率符合二级动力学方程dqe/dt=k(qe-qt)2,吸附等温线符合Langmuir方程。     

改性沸石同步深度脱氮除磷的实验研究

以氯化铝、硫酸镁为活性剂，采取高温活化，对天然沸石进行改性，并通过正交试验优化了改性工艺。以模拟二级出水为研究对象，考察了改性沸石同步去除水样中氮磷的效果及其影响因素，并对不同温度下改性沸石对磷酸盐和氨氮的吸附平衡和吸附热力学，以及脱氮除磷机理进行了探讨。结果表明，15 min后改性沸石脱氮除磷过程基本完成，其pH值范围与实际污水相符，最佳pH值为8；当投加质量浓度为0.8 g/L时，出水中氨氮浓度和总磷浓度均达到景观环境用水水质标准(GB/T 18921-2002)。改性沸石对氨氮和磷酸盐的吸附均符合Langmuir等温吸附方程。热力学参数ΔG⁰、ΔH⁰分别为正值和负值，表明该吸附是一个自发的吸热过程。     

香菇下脚料对水体中十二烷基苯磺酸钠的吸附

香菇下脚料经甲醛/硫酸混合溶液处理后制备成吸附剂。研究了吸附剂对SDBS的吸附性能,考察了溶液pH值、吸附剂粒径、初始浓度、吸附时间、浓度和温度的影响。结果表明,吸附适宜条件的为:pH 4.0,吸附时间60 min,吸附过程可以很好地用准二级动力学方程描述,吸附等温线用Langmuir方程的拟合效果优于Freundlich和Tempkin方程。在热力学研究中,ΔG0<0,ΔH0>0,ΔS0>0,表明此吸附过程是自发、吸热和熵增加的过程。     

改性膨润土对水中磷和藻类的同步去除

为快速去除富营养化水体中的磷和藻类，制备了絮凝剂-镧复合改性膨润土(聚合氯化铝铁-镧复合改性膨润土(PAFC-La)、聚合硫酸铝-镧复合改性膨润土(PAS-La)、聚合硫酸铁-镧复合改性膨润土(PFS-La)、聚合氯化铝-镧复合改性膨润土(PAC-La)),对材料进行表征，通过吸附动力学和等温吸附模型比较4种复合改性膨润土的除磷性能，并探究投药量和pH对复合改性膨润土除磷除藻的影响。结果表明，4种材料吸附磷的过程均能由准二级动力学模型和Langmuir等温吸附模型描述。其中，PAC-La的磷吸附容量最大(44.677 mg/g);投药量为300 mg/L时，总磷(TP)去除率最高的是PAC-La(94.1%),叶绿素a(Chla)去除率最高的是PFS-La(78.2%);在pH为5～10时，PAC-La除磷除藻效果受pH影响最小。实验结果表明，采用絮凝剂-镧复合改性膨润土能够同步去除富营养化水体中的磷和藻类，尤其是采用PAC-La性能最优。     

改性二氧化钛纳米管对水体中磷的吸附

利用硝酸铁对二氧化钛纳米管进行改性,并研究了改性二氧化钛纳米管对水中磷的吸附能力及吸附特征。结果表明,通过对二氧化钛纳米管的改性,提高了其对水中磷的吸附能力,磷去除率随着改性二氧化钛纳米管投加量的增加而提高,原水p H值对磷去除率影响不大;温度升高,磷去除率有所提高。进一步研究表明,改性二氧化钛纳米管对磷的吸附是一个快速吸附过程并可用准二级动力学模型进行很好的描述;热力学研究表明,改性二氧化钛纳米管对磷的吸附符合Freundlich等温吸附模型,ΔG00和ΔH00说明吸附反应是自发的吸热反应。     

改性水葫芦粉对水体中Hg~(2+)的吸附

通过二硫化碳(CS_2)对水葫芦粉进行改性,研究吸附时间、吸附剂浓度和溶液pH对改性前后水葫芦吸附溶液二价汞(Hg~(2+))的影响,并探讨其吸附动力学、热力学行为和除汞机理。结果表明:吸附剂浓度为2 g·L~(-1),溶液pH值为6,吸附时间180 min,改性水葫芦粉对Hg~(2+)浓度为2.0 mg·L~(-1)时的去除率大于93%;改性前后水葫芦粉对Hg~(2+)的吸附过程均符合拟二级动力学方程,化学吸附在整个吸附过程中起重要作用。吸附过程能够很好地用Langmuir方程拟合,吸附自由能变(ΔG)0、吸附焓变(ΔH)0、吸附熵变(ΔS)0,表明改性水葫芦粉对Hg~(2+)的吸附过程是自发的吸热过程;动力学拟合和热力学研究表明改性水葫芦粉对Hg~(2+)的吸附既有物理吸附又有化学吸附。     

富磷上清液铁接触除磷工艺及影响因素

设计了一种由铁碳合金和钝态不锈钢作为电化学腐蚀两极系统的铁接触除磷反应器,首次尝试将铁接触除磷技术用于厌氧富磷上清液的处理.通过对模拟富磷上清液除磷效果的测定与分析,详细探讨了铁接触除磷工艺的影响因素,结果表明,曝气方式宜为间歇曝气,且最优曝气/停歇时间为 60 min/30 min;在进水总磷浓度为 30～50 mg/L范围内,随着磷浓度的升高,总磷去除率随之下降;而随着曝气强度、pH值的升高及水力停留时间的延长,总磷去除率随之升高;随着水温的升高,总磷去除率有波动,水温为27℃时,总磷去除率最大.将铁接触除磷工艺运用到侧流除磷方法中,最终可使出水总磷浓度达到国家<城镇污水处理厂污染物排放标准>(GB18918-2002)中的一级(A)标准.     

改性二次锶渣吸附去除废水中的磷

以改性二次锶渣为吸附剂，研究了吸附时间、吸附剂投加量、磷初始浓度和pH值对废水中磷去除效果的影响。结果表明，当总磷浓度为10mg／L，pH为7、二次锶渣投加量为15g／L时，90min内就可使废水中磷的去除率达到95％以上，总磷浓度低于污水综合排放标准的一级标准；改性二次锶渣对磷的吸附符合Langmuir等温吸附模型及准二级动力学模型。     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Malathion-induced sublethal toxicity on the hematology of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.     

Influence of crop residues on trifluralin mineralization in a silty clay loam soil

Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day^?1 in soil with 16% A to 2.89E-02 day^?1 in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.